Indigoid vat dyestuffs



Patented Oct. 19, 1937 "lmnicom VAT DYESTUFFS Ernst StoecklimBinningen, near Basel, and Fritz Grieshaber, Riehen, near Basel, Switzerland, assignors to the firm Society of Chemical Industry in Basle, Basel, Switzerland a: Y Drawing. Application November 30, 1936, Se-

rial No. 113,530. In Switzerland December 17,

V 2- Claims.

It has been found that-indigoid vat-dyestuffs are obtained by condensing 3-h'ydroxythionaphthemes of the general formula where'in the lJWO-QF'S signify-halogen, or their reactive 2-derivatives, with components suitable for 'making indigoid dyestufisore by condensing 3- 31,

hydroxynaphthalenes of the I /oo I \CH2 s 7 general formula I e CHa wherein a: signifies halogen, or their reactive 2- derivatives, with components suitable for making indigoid dyestuffs, and halogenating the dyestuffs obtained. a 3-hydroxythionaphthenes of the foregoing general formula or their reactive 2-derivatives are,

for example 4 7-dimethyl-i5 6-dichloro-3-hydroxythionaphthene, 1 F1: 'l -dimethyl-fi bromo-G- chloro-3-hydroxythionaphthene, A 7- -dimethyl-6- chloro-3-hydroxythionaphthene and the 2- (paradimethyl-amino) -ani1 of 4:7-dimethyl-6-chloro- 3-hydroxythionaphthene.

Components suitable for making indigoid dyestuffs are, for example, 5-membered condensed ring systems, such as isatin, naphthisatin, in-

doxyl, thionaphthenequinone, hydroxythionaphthene, acenaphthenequinone,

The new dyestufis aresuitable, in particular for dyeing and printing vegetable fibre, for instance cotton, and are characterized by their purity, great covering power and very good properties of fastness. They maybe converted into leuco-ester salts by known methods.

The 3-hydroxythionaphthenes of the general formulae given or their reactive 2-derivatives may be made by various methods; for example 4:7-dimethyl-5z6 camera-3 hydroxythionaphthene may be produced as follows:

2: 5-dimethyl 3-chlorol-benzene-sulfochloride,

which boils at 132-133 C. under? 4 mm. pressure, is made by. chlorinating 2:5-dimethyl-1-benzenesuliochloride'by means of chloride in presence of a suitable halogen carrier, such as iodine, antimethyl-3-chlorol-phenylthioglycollic melting point 119-120" C. with phosphorous tri- -mony trichloride, antimony pentachloride or fer- -ric chloride.

This chloro-derivative is reduced in known manner and subsequently condensed with mono-chloracetic acid to produce 2:5-dimethyl- 3 chloro 1 phenylthioglycollic acid, which melts at 119-120 C. By treating this thioglycollic acid in, for example, chlorobenzene, with sulfuryl chloride there is obtained 2:5-dimethyl- 3:4-dichlor0-1-phenylthioglycollic acid, which crystallizes from benzene in colorless needles of melting point 110-111? C. This last-named body is treated with phosphorous trichloride and aluminium chloride or with chlorosulfonic acidto produce 4 7 -dimethyl-5 6 -dichloro-3-0xythionaphthene. It crystallizes from glacial acetic acid in colorless needles of melting point 227-228 C.

The l:7-dimethyl-6-chloro-3-hydroxythionaphtheme of melting point 115 C. is obtained, for

example, by treating the above described 2:5-diacid a of chloride and aluminium chloride in tetrachlorethane.

From the B-hydroxythionaphthenes of the aforesaid general formulae, the reactive 2-derivatives, such as the 2-anil, 2-oxime or 2-halide, may be'produc'ed in known manner by the action of a nitroso-compound, nitrous acid or halogen respectively, and from the Z-anils the 4:7-dimethyl- I 5 z6-dihalogenor .4:'T-dimethyl-G-halogenthio- "naphthenequinone is produced by treatment with warm concentrated sulfuric acid.

The following examples illustrate the invention, the parts; being by weight:

. .Example' 1 247 parts of zl-dimethyl-ii:6-dichloro-3-hy- ,droxythionaphthene and 330.5 parts of 2-(paradimethylamino) -'anil of 4-methyl-6-chloro-3-hydroxythionaphthene are heated together in 4000 parts of boiling benzene, until the condensation is finished. Filtration and drying follow. The new dyestufi of the formula is: a'red powder, soluble in concentrated sulfuric acid to a green solution and dyeing cotton in' a ;yellow vat Vivid rose tints, of very good 'fastness ,to washing, chlorine andkier-boiling; V

Example 2 r 247 parts of 4:7-dimethyl-5:6-dichloro-3-hydroxythionaphthene are dissolved in 2000 parts of chlorobenzene and the solution is mixed at using for the subsequentbromination 21 parts of bromine there is obtained a dyestufi of similar properties.

Both dyestuffs also show properties similar to 5 70 C. with a solution of 5: 7 -dibrornisatin 'chloh 9 the dyestufi obtainable as described in 5 ride made from 305 parts of 5:7-dibromisatine Example A and 250 parts of phosphorous pentachloride in Eimmple 4 V chlorobenzene in known manner. After stirring j 1 212.5 parts of 4:7-dimethyl-6-chloro-3-hyfor a shorttime the condensation is complete. droxythionaphthe'ne and 330.5 parts of 2-(para- 10 The dyestufi is filtered, washed with chlorobendimethylamino) -anil of 5-chloro-7-methyl-3- 1 zone and alcohol and dried.' It. is thena dark hydroxythionaphthene are together heated in violet powder of the formula 4000 parts of boiling alcohol until condensation CH3 is complete; Filtration and drying follow. 21 0 o o 0 parts of the dyestufi thus obtained are brominated 01- Br in the manner described in Example 3. The 15 V "brominated dyestuff of the'formula C1 C fis V V S \NH 7 "co oo 7 CH3 C1 20 soluble in concentrated sulfuric acid to a green V 7 solution and dyeing cotton in a yellow vat fast; 01 I full'blue-violet tints. v S S 'A wholly similar dyestufi is made when in this V V 7 a example 216 parts of 5:7-dichlorisatin are subis a violet powder which in its dyeing properties stituted for the 5:7-dibromisatin. is very similar to the condensation product from r Example 3 4:7- dimethyl-5:6-dichloro-S-hydroxythionapha Y thene and the Z-(para-dimethylamlno) -anil of 5- 212.5 parts of 4:'7 dimethyl-6-chloro-3-hychloro-l-methyl-3-hydroxythionaphthene.

5 droxythionaphthene are dissolved in 2000 parts In the following tablefurther examples of the dyestufis obtainable by the invention from 4:7- 80 dimethyl-5 6-dich1oro 3 hydroxythionaphthene are given:

of chlorobenzene and the solution is mixedwith one of 5:7-dibromisatinchloride, made from 305 parts of 5:7-dibromisatin and 250' parts of 'phos- I 4:7 dimethyl-5:fi-dichloro- Color of the Color otfthe Color or the V i hydroxythionaphthene and: dyestufi {uric acid dyed material (1) 2-(para-dinie'thylamino-)-anil of Red Green 'Yellow Red-violet. V a V 3-hydroxythionaphthene. I (2) 2- (para-d1methylamino-)-anil of Red Green VYellow.'. Red-violet. 40 gilchloro-3-l1ydroxythionaphl .40

- ene. (3) 2-(para-dimethy1arnino-)-anilof Red Green.. Yellow Brick-red.

gigthoxyd-hydroxythionaph- V ene. L r J r l (4) 2-(para-dimethylamino-)-anil of Violet Green Yellow;. Violet.

V 5-chloro-7-n1'ethyl 3 hydroxythionaphthene. 7 1 45 (5) 2-(para-d1methy1ammo-)-aml of Bordeaux.-. Blue-green. Yellow Bordeaux. 2:1-naphththioindoxyl. (6) 2-(para-dimothylaminm)-anii of Blue-violet Green Yellow Blue-violet. l1 chlloro 2:3 naphthtluoinoxy r V phorous pentachloride in chlorobenzene in known manner. After stirring for a short time the'condensation is complete. Filtration, washing and drying follow. 25 parts of the dyestufi thus obtained are introduced, at 6-10 0., into 900 parts The dyestufis of the table have thefo'llowlng 50 composition':-- Dyestufi No. 1

co co V of sulfuric acid of 98 per cent. strength and 9. g 01'- parts of bromine. The mixture is stirred and the 7 0:0 7 temperature raised gradually to 45-50 'C. and 0i kept at this temperature until brominatio'n is complete. The whole is then stirred with ice; OH: 7 I r a the dyestuff of the formula V Dyestufi No.2

0118 V' Jon.

co V00 V v V Br Br 0:0 5

\NH V l on, Br f H3 which has "separated is filtered, washed with r water and dried. It is a blue-violet powder, V soluble in concentrated sulfuric acid to a green e i solution and dyeing cotton in a yellow-vat fast, i f ='C 1 full blue-violet tints. V V O1 V 0 n By substituting 216 parts of 5z7-dichlorlsatin S S V 7 for the 5fl-dibromi'satin inthis example, and I 5 Dyestufi No. 4 CH3 What we claim is:

1. Indigoid vat dyestuffs 01' the general formula;

CH: V CO CO wherein :1: represents halogen.

2. The indigoid. vat dyestufi of the formula.

ERNST STO-ECKLIN. FRITZ GRIESHABER. 

